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PreprintCC BYChemRxiv

A Multi-Coordinate Carbide Ligand as the Anchor for Reactive Transition Metal Clusters: Oxidative Addition, Adduct Formation and Catalytic Hydrosilylation with a Pentanuclear Nickel Carbide Cluster

  • Manar M. Shoshani1,2,3
  • Junyang Liu3
  • Kethya Sum3
  • Samuel A. Johnson3
  1. 1Department of Chemistry
  2. 2University of Kansas
  3. 3Department of Chemistry and Biochemistry, University of Windsor, Sunset Avenue 401, Windsor, Canada, N9B 3P4
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Abstract

The reactivity of a pentanuclear carbide cluster, [( i Pr 3 P)Ni] 5 (µ 5 -C)H 4 ( 1 ), with a variety of reagents was examined. The addition of 3,5-bis(trifluoromethyl)aniline to 1 resulted in reversible N­­—H bond oxidative addition, forming [( i Pr 3 P)NiH] 5 (µ 4 -C)[N(H)C 6 H 3 ( m -CF 3 ) 2 ] ( 2 ), with a [Ni 5 ] 10+ core. Exposing 1 to neopentyl chloride produced the paramagnetic nickel carbide cluster [( i Pr 3 P)Ni] 5 (µ 5 -C)H 4 (µ 2 -Cl) ( 3 ) from a one-electron oxidation, as well as the homodimerized product 2,2,5,5-tetramethylhexane. The reaction of 1 with i Pr 3 P=S occurred with a net transfer of the sulfur to give [[( i Pr 3 P)Ni] 5 (µ 5 -C)H 4 (S) ( 4 ). When 1 was exposed to ammonia-borane, BH 3 was incorporated to form [( i Pr 3 P)Ni] 5 (µ 6 -C)H 4 (BH 3 ) ( 5 ) with a short B—C interaction. Carbide complex 1 reacts reversibly with H 2 to give tentatively assigned [( i Pr 3 P)Ni](µ 5 -C)H 6 ( 6 ). Complex 1 catalyzes the hydrosilylation of neohexene by Ph 2 SiH 2 via an intermediate tentatively assigned as the adduct [( i Pr 3 P)Ni](µ 5 -C)H 4 (H 2 SiPh 2 ) ( 7 ). All results demonstrate that despite variable coordination numbers, the carbide ligand can act as an anchoring ancillary ligand that supports geometrical flexible and atypically reactive pentanuclear clusters, even in cases like 5, where the carbide forms bonding interactions with the incoming BH 3 .

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Cite

BibTeXRIS
BibTeX
@misc{shoshani2026multicoordinate,
  title = {{A Multi-Coordinate Carbide Ligand as the Anchor for Reactive Transition Metal Clusters: Oxidative Addition, Adduct Formation and Catalytic Hydrosilylation with a Pentanuclear Nickel Carbide Cluster}},
  author = {Manar M. Shoshani and Junyang Liu and Kethya Sum and Samuel A. Johnson},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008301/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008301/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - A Multi-Coordinate Carbide Ligand as the Anchor for Reactive Transition Metal Clusters: Oxidative Addition, Adduct Formation and Catalytic Hydrosilylation with a Pentanuclear Nickel Carbide Cluster
AU  - Manar M. Shoshani
AU  - Junyang Liu
AU  - Kethya Sum
AU  - Samuel A. Johnson
PY  - 2026
DA  - 2026/09/04
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008301/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008301/v1
AB  - The reactivity of a pentanuclear carbide cluster, [( i Pr 3 P)Ni] 5 (µ 5 -C)H 4 ( 1 ), with a variety of reagents was examined. The addition of 3,5-bis(trifluoromethyl)aniline to 1 resulted in reversible N­­—H bond oxidative addition, forming [( i Pr 3 P)NiH] 5 (µ 4 -C)[N(H)C 6 H 3 ( m -CF 3 ) 2 ] ( 2 ), with a [Ni 5 ] 10+ core. Exposing 1 to neopentyl chloride produced the paramagnetic nickel carbide cluster [( i Pr 3 P)Ni] 5 (µ 5 -C)H 4 (µ 2 -Cl) ( 3 ) from a one-electron oxidation, as well as the homodimerized product 2,2,5,5-tetramethylhexane. The reaction of 1 with i Pr 3 P=S occurred with a net transfer of the sulfur to give [[( i Pr 3 P)Ni] 5 (µ 5 -C)H 4 (S) ( 4 ). When 1 was exposed to ammonia-borane, BH 3 was incorporated to form [( i Pr 3 P)Ni] 5 (µ 6 -C)H 4 (BH 3 ) ( 5 ) with a short B—C interaction. Carbide complex 1 reacts reversibly with H 2 to give tentatively assigned [( i Pr 3 P)Ni](µ 5 -C)H 6 ( 6 ). Complex 1 catalyzes the hydrosilylation of neohexene by Ph 2 SiH 2 via an intermediate tentatively assigned as the adduct [( i Pr 3 P)Ni](µ 5 -C)H 4 (H 2 SiPh 2 ) ( 7 ). All results demonstrate that despite variable coordination numbers, the carbide ligand can act as an anchoring ancillary ligand that supports geometrical flexible and atypically reactive pentanuclear clusters, even in cases like 5, where the carbide forms bonding interactions with the incoming BH 3 .
ER  -